Study On Synthesis And Performance Of 1-methyl-3,5-dininitro-1,2, 4-triazole

Nitro-triazole derivatives not only is a kind of valuable energetic materials, but also can gain broad prospect of application in synthetic drug, agricultural chemicals and light sensitive materials, so they aroused people's great attention. Triazole is one of the important new high density energetic materials because of its high strain energy associated with their five member ring. So it is important to study the synthesis and properties of triazole for the theoretical study and military applications.1-Methyl-3,5-dininitro-1,2,4-triazole was synthesized with hydrazine dihydrochloride and cyanoguanidine as starting material via three step sequence of reactions (condensation, cyclization, diazotization, nitrification, methylation),the total yield was 16.75%. The structure of MDNT was characterized by 1H NMR, ESI-MS, IR and Elemental analysis.3,5-Diamino-1,2,4-triazole was synthesized and product yield up to 96.5%, and the melting point (m.p.) was 208~210℃,its purity is more than 98.2%. Synthetic process of 3,5-Diamino-1,2,4-triazole was optimized by single factor and the orthogonal experiments. An optional production condition was obtained: reaction temperature 45~48℃, reaction time 2h , molar ratio of cyanoguanidine and hydrazine dihydrochloride 1:1.1.3,5-Dinitro-1,2,4-triazole was synthesized from 3,5-Diamino-1,2,4-triazole by diazotization and nitrification and yield was 35.72%. The melting point (m.p.) was 97~99℃,its purity is more than 99%. The influences of reaction temperature, sulfuric acid concentration, reaction time and molar ratio on the yield of 3,5-Dinitro-1,2,4-triazole was studied. An optional production condition was obtained: reaction temperature -10~ -5℃, sulfuric acid concentration 0.68mol/L, reaction time 3h and molar ratio of sulfuric acid and 3,5-Diamino-1,2,4-triazole 5:1, and the whole system response was mild, no risk agglomerate, safer, and rate is higher. Sodium salt, silver salt and ammonium salt was synthesized from intermediate 3,5-Dinitro-1,2,4-triazole. Respectively, their melting points were 225~227℃, 247~249℃and 208~210℃.The target product 1-Methyl-3,5-dininitro-1,2,4-triazole was synthesized by methylation and yield was 48.59%. The melting point (m.p.) was 94~96℃,its purity is more than 99%. Synthetic process of 1-Methyl-3,5-dininitro-1,2,4-triazole was optimized by single factor and the orthogonal experiments. An optional production condition was obtained: reaction temperature 45~48℃, reaction time 3.8~4.1h, molar ratio of dimethyl sulfate and 3,5-Dininitro-1,2,4-triazole 4.2:1.Density is 1.62 g/cm~3 by methods of density bottle, detonation is 7486m/s, and exlosion pressure is 26.35GPa by experience of kamlet formula, the impact sensitivity (5kg) H50 is 98cm. The DSC-TG techniques were used to study the thermal behavior of 1-Methyl-3,5-dininitro-1,2,4-triazole, results show that they have good thermal stability.